Systems and methods for nanofunctionalization of powders

ABSTRACT

Some variations provide a system for producing a functionalized powder, comprising: an agitated pressure vessel; first particles and second particles contained within the agitated pressure vessel; a fluid contained within the agitated pressure vessel; an exhaust line for releasing the fluid from the agitated pressure vessel; and a means for recovering a functionalized powder containing the second particles disposed onto surfaces of the first particles. A preferred fluid is carbon dioxide in liquefied or supercritical form. The carbon dioxide may be initially loaded into the pressure vessel as solid carbon dioxide. The pressure vessel may be batch or continuous and is operated under reaction conditions to functionalize the first particles with the second particles, thereby producing a functionalized powder, such as nanofunctionalized metal particles in which nanoparticles act as grain refiners for a component ultimately produced from the nanofunctionalized metal particles. Methods for making the functionalized powder are also disclosed.

PRIORITY DATA

This patent application is a non-provisional application with priorityto of U.S. Provisional Patent App. No. 62/540,616, filed on Aug. 3,2017, which is hereby incorporated by reference herein. This patentapplication is also a continuation-in-part application of U.S. Pat. No.11,052,460, issued on Jul. 6, 2021, which has priority to U.S.Provisional Patent App. No. 62/452,989, filed on Feb. 1, 2017, and toU.S. Provisional Patent App. No. 62/463,952, filed on Feb. 27, 2017,each of which is hereby incorporated by reference herein.

FIELD OF THE INVENTION

The present invention generally relates to methods and apparatus forfunctionalizing metal powders or other powders, and functionalizedmaterials produced.

BACKGROUND OF THE INVENTION

The assembly of nanoparticles onto substrates is relevant for a widevariety of applications. There are known coating methods available todeposit nanoparticles. The methods differ by their ability to controlparticle packing density and layer thickness, the ability to usedifferent particles, and the complexity of the method andinstrumentation needed.

Metal-based additive manufacturing, or three-dimensional (3D) printing,has applications in many industries, including the aerospace andautomotive industries. Building up metal components layer by layerincreases design freedom and manufacturing flexibility, thereby enablingcomplex geometries while eliminating traditional economy-of-scaleconstraints. However, currently only a few alloys, the most relevantbeing AlSi10Mg, TiAl6V4, CoCr, and Inconel 718, can be reliably printed.The vast majority of the more than 5,500 alloys in use today cannot beadditively manufactured because the melting and solidification dynamicsduring the printing process lead to intolerable microstructures withlarge columnar grains and cracks. 3D-printable metal alloys are limitedto those known to be easily weldable. The limitations of the currentlyprintable alloys, especially with respect to specific strength, fatiguelife, and fracture toughness, have hindered metal-based additivemanufacturing. See Martin et al., “3D printing of high-strengthaluminium alloys” Nature vol. 549, pages 365-369, which is herebyincorporated by reference.

In particular, during solidification of many alloys, the primaryequilibrium phase solidifies first at a different composition from thebulk liquid. This mechanism results in solute enrichment in the liquidnear the solidifying interface, locally changing the equilibriumliquidus temperature and producing an unstable, undercooled condition.As a result, there is a breakdown of the solid-liquid interface leadingto cellular or dendritic grain growth with long channels ofinterdendritic liquid trapped between solidified regions. As temperatureand liquid volume fraction decrease, volumetric solidification shrinkageand thermal contraction in these channels produces cavities and hottearing cracks which may span the entire length of the columnar grainand can propagate through additional intergranular regions.

Fine equiaxed microstructures accommodate strain in the semi-solid stateby suppressing coherency that locks the orientation of these soliddendrites and promotes tearing. Producing equiaxed structures requireslarge amounts of undercooling, which has thus far proven difficult inadditive processes where high thermal gradients arise from rastering ofa direct energy source in an arbitrary geometric pattern.

What is needed is an approach to control solidification microstructureby promoting nucleation of new grains of metal alloys, such asadditively manufactured metal alloys. Use of nanoparticles in additivemanufacturing has been described, but uniformity and scale-up have beendifficult. Systems (apparatus) and methods to incorporate nanoparticlesinto metal or metal alloy powders are desired.

SUMMARY OF THE INVENTION

The present invention addresses the aforementioned needs in the art, aswill now be summarized and then further described in detail below.

Some variations of the invention provide a system for producing afunctionalized powder, the system comprising:

-   (a) an agitated pressure vessel;-   (b) a thermal-control unit (e.g., a heater) disposed in thermal    communication with the agitated pressure vessel;-   (c) a plurality of first particles contained within the agitated    pressure vessel;-   (d) a plurality of second particles contained within the agitated    pressure vessel;-   (e) a fluid contained within the agitated pressure vessel;-   (f) an exhaust line for releasing the fluid from the agitated    pressure vessel; and-   (g) a means for recovering a functionalized powder containing the    second particles disposed onto surfaces of the first particles.

In some embodiments, the fluid is a non-flammable fluid. The fluid maybe a liquid, a gas, or a combination thereof.

In various embodiments, the fluid is selected from the group consistingof carbon dioxide, nitrous oxide, C₁-C₄ hydrocarbons (e.g., methane,ethane, ethylene, propane, propylene, or n-butane), C₁-C₄ oxygenates(e.g., methanol, ethanol, or acetone), and combinations thereof.

In some embodiments, the fluid includes or consists essentially ofcarbon dioxide (CO₂). The carbon dioxide may be in a vapor state withinthe agitated pressure vessel. Alternatively, or additionally, the carbondioxide may be in a liquid state within the agitated pressure vessel. Incertain embodiments, the carbon dioxide is in a supercritical statewithin the agitated pressure vessel. When the fluid includes carbondioxide, the system optionally comprises a means for introducing solidcarbon dioxide into the agitated pressure vessel.

In some embodiments, the exhaust line includes a filter to capture thefirst particles, the second particles, and/or the functionalized powder.

In some embodiments, the system further comprises a safety release linethat is activated when the pressure within the agitated pressure vesselreaches a predetermined pressure, such as 200 bar.

The system may further comprise a separate container disposed in flowcommunication with the exhaust line, for receiving fluid released fromthe agitated pressure vessel. The separate container may be a drumfilled with water or oil, for example.

The system preferably includes a control subsystem for adjustingtemperature, pressure, residence time, and/or agitation within theagitated pressure vessel.

The system may be a batch apparatus, a continuous apparatus, asemi-continuous apparatus, or a combination thereof.

In some embodiments, the first particles are selected from the groupconsisting of metal particles, intermetallic particles, ceramicparticles, and combinations thereof. For example, the first particlesmay contain one or more metals selected from the group consisting ofaluminum, iron, nickel, copper, titanium, magnesium, zinc, silicon,lithium, silver, chromium, manganese, vanadium, bismuth, gallium, lead,and combinations thereof. The first particles may have an averagefirst-particle size from about 1 micron to about 1 millimeter, forexample.

In some embodiments, the second particles are selected from the groupconsisting of metal particles, intermetallic particles, ceramicparticles, and combinations thereof. For example, the second particlesmay contain one or more elements selected from the group consisting ofzirconium, tantalum, niobium, titanium, and oxides, nitrides, hydrides,carbides, or borides thereof, and combinations of the foregoing. Thesecond particles may have an average second-particle size from about 1nanometer to about 100 microns, for example.

In certain embodiments of the invention, the recovered functionalizedpowder is a nanofunctionalized metal powder.

Other variations of the invention provide a system for producing afunctionalized powder, wherein the system does not (yet) physicallycontain the first particles, the second particles, and/or the fluid, thesystem comprising:

-   (a) an agitated pressure vessel;-   (b) a thermal-control unit (e.g., a heater) disposed in thermal    communication with the agitated pressure vessel;-   (c) a means for introducing a plurality of first particles into the    agitated pressure vessel, such as by adding the first particles to a    batch vessel, or pumping the first particles into continuous vessel;-   (d) a means for introducing a plurality of second particles into the    agitated pressure vessel, such as by adding the second particles to    a batch vessel, or pumping the second particles into continuous    vessel, with or separate from the first particles;-   (e) a means for introducing a fluid into the agitated pressure    vessel, such as by adding the fluid directly to the pressure vessel    or by introducing a fluid precursor (e.g., solid CO₂) into the    pressure vessel;-   (f) an exhaust line for releasing the fluid from the agitated    pressure vessel, wherein the release may be continuous,    intermittent, or triggered at a predetermined pressure, for example;    and-   (g) a means for recovering a functionalized powder containing the    second particles disposed onto surfaces of the first particles,    wherein the recovering may include isolating from a batch vessel, or    pumping out of a continuous vessel, for example.

Some variations of the invention provide a method for producing afunctionalized powder, the method comprising:

-   introducing a plurality of first particles into an agitated pressure    vessel;-   introducing a plurality of second particles into the agitated    pressure vessel;-   introducing a fluid into the agitated pressure vessel, wherein the    fluid dissolves or suspends at least one of the first particles or    the second particles;-   in the agitated pressure vessel, reacting the second particles with    the first particles to generate a functionalized powder containing    the second particles disposed onto surfaces of the first particles;-   releasing the fluid from the agitated pressure vessel; and    recovering the functionalized powder from the agitated pressure    vessel.

In some methods, the fluid is selected from the group consisting ofcarbon dioxide, nitrous oxide, C₁-C₄ hydrocarbons, C₁-C₄ oxygenates, andcombinations thereof.

In some embodiments, the fluid includes carbon dioxide in a vapor stateand/or a liquid state within the agitated pressure vessel. In certainembodiments, the fluid includes carbon dioxide in a supercritical statewithin the agitated pressure vessel.

Optionally, solid carbon dioxide may be introduced into the agitatedpressure vessel. The solid carbon dioxide melts within the agitatedpressure vessel to form carbon dioxide in vapor form and/or liquid form.During reactor operation, the CO₂ may be in vapor, liquid, and/orsupercritical form, but should not be primarily in solid form.

In some embodiments, the reaction for reacting the second particles withthe first particles is conducted at a reaction temperature from about10° C. to about 200° C. In these or other embodiments, the reaction isconducted at a reaction pressure from about 2 bar to about 200 bar. Thereaction may be conducted for a reaction time from about 10 minutes toabout 50 hours, for example.

In some embodiments, the method is operated in batch. In otherembodiments, the method is operated continuously or semi-continuously.

In some methods, the first particles are selected from the groupconsisting of metal particles, intermetallic particles, ceramicparticles, and combinations thereof

In certain methods, the first particles contain one or more metalsselected from the group consisting of aluminum, iron, nickel, copper,titanium, magnesium, zinc, silicon, lithium, silver, chromium,manganese, vanadium, bismuth, gallium, lead, and combinations thereof.

In some methods, the second particles are selected from the groupconsisting of metal particles, intermetallic particles, ceramicparticles, and combinations thereof.

In certain methods, the second particles contain one or more elementsselected from the group consisting of zirconium, tantalum, niobium,titanium, and oxides, nitrides, hydrides, carbides, or borides thereof,and combinations of the foregoing.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is an exemplary system to produce nanofunctionalized metalpowder, in some embodiments of the invention.

FIG. 2 is a flowchart for an exemplary method of using the system ofFIG. 1 to produce a nanofunctionalized metal powder, in someembodiments.

FIG. 3 is a scanning electron microscopy (SEM) image of Al 7075 powdernanofunctionalized with TiB₂ nanoparticles (scale bar 5 μm), in someembodiments.

FIG. 4 is an SEM image of Al 7075 powder nanofunctionalized with WC(tungsten carbide) nanoparticles (scale bar 5 μm), in some embodiments.

FIG. 5 is an SEM image of AlSi10Mg powder nanofunctionalized with WCnanoparticles (scale bar 5 μm), in some embodiments.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

The compositions, structures, systems, and methods of the presentinvention will be described in detail by reference to variousnon-limiting embodiments.

This description will enable one skilled in the art to make and use theinvention, and it describes several embodiments, adaptations,variations, alternatives, and uses of the invention. These and otherembodiments, features, and advantages of the present invention willbecome more apparent to those skilled in the art when taken withreference to the following detailed description of the invention inconjunction with the accompanying drawings.

As used in this specification and the appended claims, the singularforms “a,” “an,” and “the” include plural referents unless the contextclearly indicates otherwise. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as is commonlyunderstood by one of ordinary skill in the art to which this inventionbelongs.

Unless otherwise indicated, all numbers expressing conditions,concentrations, dimensions, and so forth used in the specification andclaims are to be understood as being modified in all instances by theterm “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that may vary depending at least upona specific analytical technique.

The term “comprising,” which is synonymous with “including,”“containing,” or “characterized by” is inclusive or open-ended and doesnot exclude additional, unrecited elements or method steps. “Comprising”is a term of art used in claim language which means that the named claimelements are essential, but other claim elements may be added and stillform a construct within the scope of the claim.

As used herein, the phrase “consisting of” excludes any element, step,or ingredient not specified in the claim. When the phrase “consists of”(or variations thereof) appears in a clause of the body of a claim,rather than immediately following the preamble, it limits only theelement set forth in that clause; other elements are not excluded fromthe claim as a whole. As used herein, the phrase “consisting essentiallyof” limits the scope of a claim to the specified elements or methodsteps, plus those that do not materially affect the basis and novelcharacteristic(s) of the claimed subject matter.

With respect to the terms “comprising,” “consisting of,” and “consistingessentially of,” where one of these three terms is used herein, thepresently disclosed and claimed subject matter may include the use ofeither of the other two terms, except when used in Markush groups. Thusin some embodiments not otherwise explicitly recited, any instance of“comprising” may be replaced by “consisting of” or, alternatively, by“consisting essentially of.”

The present invention is premised on scalable and cost-effective systemsfor powder functionalization without requiring flammable solvents. Thefunctionalized powders may be used in additive manufacturing or as rawmaterials in other applications that can benefit from powderfunctionalization.

Some variations of the invention provide a system for producing afunctionalized powder, the system comprising:

-   (a) an agitated pressure vessel;-   (b) a thermal-control unit, such as a heater, disposed in thermal    communication with the agitated pressure vessel;-   (c) a plurality of first particles contained within the agitated    pressure vessel;-   (d) a plurality of second particles contained within the agitated    pressure vessel;-   (e) a fluid contained within the agitated pressure vessel;-   (f) an exhaust line for releasing the fluid from the agitated    pressure vessel; and-   (g) a means for recovering a functionalized powder containing the    second particles disposed onto surfaces of the first particles.

The choice of fluid(s) will depend on compatibility of fluid with thefirst and second particles. In some embodiments, the fluid dissolves orsuspends at least one of the components. Van der Waals forces, chemicalbonds, physical adsorption, or other forces may cause the secondparticles to be retained on surfaces of the first particles. The fluidmay have a lower surface energy than the first particles, the secondparticles, or both of these. When this fluid is released from a mixtureof first and second particles, the latter may be drawn by capillaryforces to surfaces of first particles, in some embodiments.

The fluid may be a liquid, a gas, or a combination thereof. In variousembodiments, the fluid is selected from the group consisting of carbondioxide (CO₂) nitrous oxide (N₂O), C₁-C₄ hydrocarbons (e.g., methane,ethane, ethylene, propane, propylene, or n-butane), C₁-C₄ oxygenates(e.g., methanol, ethanol, or acetone), and combinations thereof. Forpurposes of this disclosure, derivatives of hydrocarbons or oxygenates,in which one or more hydrogen atoms are replaced by other elements orfunctional groups, are included. For example, replacing each H atom witha Cl atom in methane results in carbon tetrachloride (CCl₄), which maybe used as a fluid, in certain embodiments.

In some embodiments, the fluid is a non-flammable fluid. A“non-flammable fluid” as meant herein is a fluid that does not combustin air at atmospheric pressure. Exemplary non-flammable fluids are CO₂,N₂O, and CCl₄. In some embodiments, an ordinarily flammable substance(such as propane) is made to be non-flammable in a mixture with diluentgas, such as Ar or N₂.

In some embodiments, the fluid includes or consists essentially ofcarbon dioxide. The carbon dioxide may be in a vapor state within theagitated pressure vessel. Alternatively, or additionally, the carbondioxide may be in a liquid state within the agitated pressure vessel. Incertain embodiments, the carbon dioxide is in a supercritical statewithin the agitated pressure vessel. When the fluid includes carbondioxide, the system optionally comprises a means for introducing solidcarbon dioxide (also known as dry ice) into the agitated pressurevessel.

Employing a liquefied or supercritical CO₂ solution of particles allowsmixing of the powder particles, with the benefit of not requiring aflammable solvent (i.e., mixing is conducted in an atmosphere incapableof igniting). After functionalization, the CO₂ may be vented off quicklyand recycled, thereby eliminating waste while also drying the powder.Following removal of liquefied or supercritical CO₂, Van der Waalsforces, chemical bonds, physical adsorption, or other forces may causethe nanoparticles to be retained on surfaces of the powder particles.

The agitated pressure vessel is operated under effective reactionconditions to dispose the second particles onto surfaces of the firstparticles, regardless of mechanism. The effective reaction conditionsinclude selection of temperature, pressure, residence time (i.e.,reaction time), and agitation, or ranges of such parameters, such thatthe desired powder functionalization takes place at least to someextent.

Effective temperatures may range from about 10° C. to about 200° C.,such as from about 25° C. to about 100° C., e.g. about 30° C., 35° C.,40° C., 50° C., 60° C., 70° C., 80° C., or 90° C. When the desiredreaction temperature is relatively low, such as about 30° C. or less,the thermal-control unit may be omitted. The thermal-control unit may bea heater, which may be provided in various forms such as (but notlimited to) hot oil, steam jacket, heat tape, or an oven, for example.The thermal-control unit may be a combined heater/cooler or aheat-transfer medium that enables the reactor to be maintained at adesired temperature.

Effective pressures may range from about 2 bar to about 200 bar, such asfrom about 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 bar.

Effective residence times may range from about 1 minute to about 100hours, such as from about 10 minutes to about 50 hours, e.g. about 0.5,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, or 25 hours.

Selection of temperature and pressure will generally depend on choice offluid, and one skilled in the art can consult the phase diagram of theselected fluid so that the fluid, during particle functionalization,remains in the desired phase(s) such as a liquid phase or thesupercritical phase. Selection of time will generally depend on thenature of the first and second particles and the kinetics associatedwith functionalization, which depends on selected temperature andpressure. There is therefore an interrelationship among time,temperature, and pressure, as is common with chemical reactions.

The pressure vessel may be agitated in a variety of ways. In someembodiments, the pressure vessel is disposed in physical communicationwith an external vibrating motor that physically vibrates the pressurevessel to mix the contents. In some embodiments, the pressure vessel isconfigured with a stirring mechanism such as an internal impeller orpaddle. In some embodiments, the pressure vessel is agitated by rollingor tumbling the pressure vessel in an automated manner within theoverall system. In some embodiments, the pressure vessel is agitated viacontinuous recycling of fluid that is pumped out of and back into thepressure vessel. For example, a continuous purge of fluid may be takenfrom the pressure vessel, separate from or integrated with the exhaustline, from the top and reinjected into the bottom of the pressure vesselto enhance the mixing efficiency. In similar embodiments, continuousrecirculation of an inert gas (such as Ar or N₂) through the pressurevessel may be employed to enhance the mixing efficiency. Combinations ofany of these agitation techniques, or others (e.g., sonication), may beemployed in certain embodiments.

Effective agitation ranges may vary and may be characterized by anoutput associated with the selected agitation means. For example, in thecase of an external vibrating motor, the vibration frequency may bemonitored or controlled. In the case of an internal impeller, theimpeller revolution frequency (e.g., revolutions per minute, rpm) may bemonitored or controlled. In the case of a continuous purge andreinjection of fluid or another gas, the recycle flow rate may bemonitored or controlled, and so on.

For any type of agitation, the fluid Reynolds Number (Re) may bemonitored, estimated, or controlled, such as by use of tracers tomeasure velocity distribution within the pressure vessel. The Re may bebased on the vessel diameter or on the impeller diameter in the case ofan internal impeller, for example. In various embodiments, an effectiveinternal Re may be from about 100 to about 10,000, such as from about1,000 to about 5,000. The flow pattern within the pressure vessel may belaminar or turbulent.

The specific agitation rate is not regarded as critical to theinvention, and one skilled in the art will be able to employ aneffective agitation rate. While a non-agitated pressure vessel (Re=0)may in principle be employed, it is not preferred due to theheat-transfer and mass-transfer limitations arising from lack ofagitation. This can potentially be overcome by excessively longresidence times to allow the necessary particle diffusion, but thatleads to larger vessels and higher costs.

The system preferably includes a reactor control subsystem for adjustingtemperature, pressure, residence time, and/or agitation within theagitated pressure vessel. A reactor control subsystem may be configuredto vary parameters during reaction, such as over a prescribed protocol,or in response to measured variables. For example, an unintended changein vessel pressure may be compensated by a change in vessel temperatureand/or residence time. As another example, temperature may be maintainedconstant (isothermal operation) or pressure may be maintained constant(isobaric operation). The reactor control subsystem may utilizewell-known control logic principles, such as feedback control andfeedforward control. Control logic may incorporate results from previousexperiments or production campaigns. One example of a reactor controlsubsystem is MasterLogic Programmable Logic Controller from Honeywell(Morris Plains, N.J., U.S.).

After the desired reactive functionalization has taken place, thepressure within the pressure vessel may be reduced or fully released(i.e. down to atmospheric pressure) by opening a valve to allow thefluid to exit out the exhaust line. The pressure vessel may be openedand the functionalized powder may be allowed to dry before recovery fromthe vessel. In some embodiments, an inert gas is swept through thevessel following such pressure release, to assist in drying by removingresidual fluid, for example. Alternatively, or additionally, thefunctionalized powder may be recovered from the pressure vessel andintroduced into a separate unit for drying or other treatment. In someembodiments, such as when the system is continuous or when automatedbatch production is desired, the pressure vessel may be configured witha large valve and optionally a bottom scraper or other means to recoverthe functionalized powder from the pressure vessel.

The system may further comprise a separate container disposed in flowcommunication with the exhaust line, for receiving fluid released fromthe agitated pressure vessel. The separate container may be a drumfilled with water or oil, for example.

Particles or functionalized powder preferably should not be allowed toflow to the separate container. Depending on the specific system design,particles and functionalized powder may end up in the exhaust line. Insome embodiments, the exhaust line includes a filter to capture thefirst particles, the second particles, and/or the functionalized powder.The filter may be designed to remove particles that are at least thesize of nanoparticles, at least the size of microparticles, or someother filter size. In other embodiments, a centrifuge or otherseparation means is utilized in the exhaust line, to recover thefiltered solid material. The recovered solid material (e.g., fromfiltering, centrifuging, or other means) may then be returned to thepressure vessel, either continuously or intermittently, or discarded.

In some embodiments, the system further comprises a safety release linethat is activated when the pressure within the agitated pressure vesselreaches or exceeds a predetermined pressure, such as a pressure selectedfrom 25 bar to 300 bar (e.g., 200 bar) that is higher than the desiredreaction pressure within the pressure vessel.

Other safety considerations may be applied to the system. The reactorcontrol subsystem mentioned above may include protective devices thatautomatically shut down the operation, when the temperature or pressureexceeds a maximum value. Practical safety-related design may be builtinto the system as well. For example, the entire pressure vessel may bedisposed within a sand bath contained in a suitable container. Thoseskilled in the art will understand how to design safe pressure vesselsand systems employing them.

The volume of the pressure vessel may vary widely, such as (but notlimited to) from about 0.1 liter to about 1,000 liters, e.g. from about1 liter to about 100 liters.

The system may be a batch apparatus, a continuous apparatus, asemi-continuous apparatus, or a combination thereof. A batch apparatusincludes a batch reactor, such as a pressure vessel. An example of apressure vessel as a batch reactor is depicted in FIG. 1 , furtherdiscussed below. A continuous apparatus includes a high-pressure reactorconfigured for a continuous feed of first and second particles and acontinuous feed of fluid. The high-pressure reactor may be a tank orvessel in which the particles and fluid are continuously stirred, or atubular reactor in which the particles and fluid are in plug flow (whichis well-mixed, i.e. agitated, in the radial direction), or anintermediate mixing pattern between these extremes. A continuoushigh-pressure reactor may be horizontal or vertical, and may beconfigured for cocurrent flow of particles and fluid, or countercurrentflow of particles and fluid, or countercurrent flow of fluid and firstparticles against flow of second particles, and so on. An example of asemi-continuous apparatus is the batch apparatus of FIG. 1 modified forcontinuous recirculating flow of fluid, or a continuously stirred tankwith intermittent feed of particles and/or intermittent release offluid, for example.

In some embodiments, the first particles are selected from the groupconsisting of metal particles, intermetallic particles, ceramicparticles, and combinations thereof. For example, the first particlesmay contain one or more metals selected from the group consisting ofaluminum, iron, nickel, copper, titanium, magnesium, zinc, silicon,lithium, silver, chromium, manganese, vanadium, bismuth, gallium, lead,and combinations thereof.

The first particles may have an average first-particle size from about 1micron to about 1 millimeter, for example. In various embodiments, thefirst particles have an average first-particle size of about 1, 2, 5,10, 25, 50, 100, 200, 300, 400, 500, 600, 700, 800, or 900 microns.

In some embodiments, the second particles are selected from the groupconsisting of metal particles, intermetallic particles, ceramicparticles, and combinations thereof. For example, the second particlesmay contain one or more elements selected from the group consisting ofzirconium, tantalum, niobium, titanium, and oxides, nitrides, hydrides,carbides, or borides thereof, and combinations of the foregoing.

The second particles may have an average second-particle size from about1 nanometer to about 100 microns, for example. In various embodiments,the second particles have an average second-particle size of about 1, 2,5, 10, 25, 50, 100, 200, 300, 400, 500, 600, 700, 800, or 900nanometers, or about 1, 2, 5, 10, 20, 30, 40, 50, or 75 microns.

In certain embodiments of the invention, the recovered functionalizedpowder is a nanofunctionalized metal powder. In a nanofunctionalizedmetal powder, the average second-particle size is 1000 nanometers orless.

Other variations of the invention provide a system for producing afunctionalized powder, wherein the system does not (yet) physicallycontain the first particles, the second particles, and/or the fluid, thesystem comprising:

-   (a) an agitated pressure vessel;-   (b) a thermal-control unit disposed in thermal communication with    the agitated pressure vessel;-   (c) a means for introducing a plurality of first particles into the    agitated pressure vessel, such as by adding the first particles to a    batch vessel, or pumping the first particles into continuous vessel;-   (d) a means for introducing a plurality of second particles into the    agitated pressure vessel, such as by adding the second particles to    a batch vessel, or pumping the second particles into continuous    vessel, with or separate from the first particles;-   (e) a means for introducing a fluid into the agitated pressure    vessel, such as by adding the fluid directly to the pressure vessel    or by introducing a fluid precursor (e.g., inserting solid CO₂ prior    to starting the reaction) into the pressure vessel;-   (f) an exhaust line for releasing the fluid from the agitated    pressure vessel, wherein the release may be continuous,    intermittent, or triggered at a predetermined pressure, for example;    and-   (g) a means for recovering a functionalized powder containing the    second particles disposed onto surfaces of the first particles,    wherein the means for recovering may include isolating from a batch    vessel, or pumping out of a continuous vessel, for example.

The following description, with reference to FIG. 1 , is an exemplarysystem for producing a functionalized powder. This design can be adaptedusing known chemical-engineering principles to any scale system forcontinued production of larger volumes of functionalized powders. Theexample system of FIG. 1 is capable of containing a controlled volume ofcarbon dioxide above its critical point, and is capable of safelyimmersing metal powders in a supercritical carbon dioxide environment.

FIG. 1 is a process-flow diagram of a particle functionalization system100. A pressure vessel 105 may be a metal vessel manufactured by ParrInstrument Company (Moline, Ill., US) with an interior volume of 1liter. The pressure vessel 105 is disposed within an outer container160, in some embodiments. System 100 is a closed environment to avoidthe unintended escape of particles from the system.

During functionalization, the pressure vessel 105 contains metal powdersas the first particles, and metal or non-metal nanopowders as the secondparticles. The selected fluid is carbon dioxide, in this example. Thecarbon dioxide, metal powder, and nanopowder may be enclosed in thepressure vessel 105 in a batchwise manner, i.e. prior to closing up thepressure vessel 105 for operation.

The carbon dioxide may be sealed in the pressure vessel 105 in its solidstate, along with packing the particles into the pressure vessel 105.The packing may be done in an inert atmosphere, such as with argon ornitrogen. The solid carbon dioxide undergoes sublimation to form CO₂gas, prior to operation of the pressure vessel. Depending on the time tobegin operation, some of the solid CO₂ may melt into liquid CO₂ orconvert to supercritical CO₂ without first sublimating into vapor.Regardless of the form of CO₂ added to the pressure vessel 105, thetemperature and pressure during functionalization will dictate thephase(s) of CO₂ present in the pressure vessel 105. Depending on theloading of carbon dioxide, the volume occupied by metal powder, and theamount of heating, the carbon dioxide in situ may be in its liquid, gas,or supercritical regime, which may be predicted by an appropriateequation of state dependent upon the instantaneous temperature andpressure.

The pressure vessel 105 is attached to a heating element 110. Theheating element 110 (e.g., heat tape) is monitored by a thermocouple 150to bring the vessel 105 to a desired temperature, while a pressuretransducer 125 monitors the internal vessel pressure. The pressurevessel 105 may be insulated to maintain adiabatic operation or at leastminimize heat losses. External cooling of the pressure vessel 105 may beemployed in certain embodiments in which functionalization isexothermic, to help control reaction temperature.

A vibrating motor 115 is directly attached to the surface of the vessel105 to provide adequate mixing of the metal powder and nanopowder withinthe carbon dioxide environment. The motor 115 is attached to electricalsource 120 to drive the motor 115. Instead of vibration, or in addition,the vessel 105 may be agitated by other known agitation means such asstirring, rolling, tumbling, etc.

The pressure vessel 105 of FIG. 1 includes a general inlet/outlet at thetop of the vessel. The general inlet/outlet is directly attached to apressure transducer 125, which has an electrical readout of 0-5 VDC tobe calibrated and used in LabVIEW (National Instruments Corporation,Austin, Tex., U.S.), for example. The pressure transducer 125 is in linewith a pneumatically controlled valve 135, which will open such as when5-15 bar air pressure is applied to its actuator. The actuator may becontrolled remotely by an air compressor 130. When the pneumaticallycontrolled valve 135 is opened, a partially opened needle valve 140restricts the flow rate of fluid out of the system. A flexible stainlesssteel braided hose may make this connection.

The pneumatically controlled valve 135 keeps the vessel release line 145closed during standard operation. Upon completed functionalization, orwhen desired by an operator, the valve 135 may be opened remotely byapplying a change in pressure. The flow of the fluid and particlesthrough the release line 145 may be limited by the needle valve 140. Thereleased fluid, CO₂ in this example, may be fed via release line 145into a drum of water or another container (not shown). An over-pressureline 155 may be routed to the same drum of water or other container, orotherwise purged from the system.

The over-pressure line 155 is primarily for safety and is not normallyin operation. In some embodiments, an over-pressure rupture disk or anautomated pressure-relief valve is disposed in flow communication withan orifice of the pressure vessel. The over-pressure rupture disk orautomated pressure-relief valve may be connected to a line that leads tothe same container (e.g., 55-gallon drum of water) that receives thefluid release line. The over-pressure rupture disk or automatedpressure-relief valve may be configured to burst or release at anydesired pressure, such as a pressure selected from 100-300 bar (e.g.,200 bar). For further safety precaution, the entire vessel 105 may besubmerged in a 55-gallon drum filled with sand, as the outer container160, for example. A sand drum 160 is also for safety and may be omittedwhen the pressure vessel 105 is properly prevented from explosion.

Some variations of the invention provide a method for producing afunctionalized powder, the method comprising:

-   introducing a plurality of first particles into an agitated pressure    vessel;-   introducing a plurality of second particles into the agitated    pressure vessel;-   introducing a fluid into the agitated pressure vessel, wherein the    fluid dissolves or suspends at least one of the first particles or    the second particles;-   in the agitated pressure vessel, reacting the second particles with    the first particles to generate a functionalized powder containing    the second particles disposed onto surfaces of the first particles;-   releasing the fluid from the agitated pressure vessel; and-   recovering the functionalized powder from the agitated pressure    vessel.

In some methods, the fluid is selected from the group consisting ofcarbon dioxide, nitrous oxide, C₁-C₄ hydrocarbons, C₁-C₄ oxygenates, andcombinations thereof.

In some embodiments, the fluid includes carbon dioxide in a vapor stateand/or a liquid state within the agitated pressure vessel. In certainembodiments, the fluid includes carbon dioxide in a supercritical statewithin the agitated pressure vessel.

Optionally, solid carbon dioxide may be introduced into the agitatedpressure vessel. The solid carbon dioxide melts within the agitatedpressure vessel to form carbon dioxide in vapor form and/or liquid form.During reactor operation, the CO₂ may be in vapor, liquid, and/orsupercritical form, but should not be primarily in solid form.

In some embodiments, the reaction for reacting the second particles withthe first particles is conducted at a reaction temperature from about10° C. to about 200° C. In these or other embodiments, the reaction isconducted at a reaction pressure from about 2 bar to about 200 bar. Thereaction may be conducted for a reaction time from about 10 minutes toabout 50 hours, for example.

In some embodiments, the method is operated in batch. In otherembodiments, the method is operated continuously or semi-continuously.

In some methods, the first particles are selected from the groupconsisting of metal particles, intermetallic particles, ceramicparticles, and combinations thereof. In certain methods, the firstparticles contain one or more metals selected from the group consistingof aluminum, iron, nickel, copper, titanium, magnesium, zinc, silicon,lithium, silver, chromium, manganese, vanadium, bismuth, gallium, lead,and combinations thereof.

In some methods, the second particles are selected from the groupconsisting of metal particles, intermetallic particles, ceramicparticles, and combinations thereof. In certain methods, the secondparticles contain one or more elements selected from the groupconsisting of zirconium, tantalum, niobium, titanium, and oxides,nitrides, hydrides, carbides, or borides thereof, and combinations ofthe foregoing.

FIG. 2 is a flowchart for an exemplary method of using the system ofFIG. 1 to produce a functionalized powder, in some embodiments. Thesystem of FIG. 1 may be operated according to the method of FIG. 2 . Thesystem of FIG. 1 and the method of FIG. 2 are suitable for producing theexemplary functionalized metal powders shown in FIGS. 3, 4 , and/or 5.

FIG. 3 is a scanning electron microscopy (SEM) image of Al 7075 powder310 nanofunctionalized with discontinuous TiB₂ nanoparticles 320 (scalebar 5 μm), resulting in functionalized powder 300. FIG. 4 is an SEMimage of Al 7075 powder 410 nanofunctionalized with discontinuous WC(tungsten carbide) nanoparticles 420 (scale bar 5 μm), resulting infunctionalized powder 400. FIG. 5 is an SEM image of AlSi10Mg powder 510nanofunctionalized with discontinuous WC nanoparticles 520 (scale bar 5μm), resulting in functionalized powder 500.

Some embodiments of the present invention utilize materials, methods,and principles described in commonly owned U.S. patent application Ser.No. 15/209,903, filed Jul. 14, 2016, U.S. patent application Ser. No.15/808,872, filed Nov. 9, 2017, U.S. patent application Ser. No.15/808,877, filed Nov. 9, 2017, and/or U.S. patent application Ser. No.15/808,878, filed Nov. 9, 2017, each of which is hereby incorporated byreference herein. This specification also hereby incorporates byreference herein Martin et al., “3D printing of high-strength aluminiumalloys” Nature vol. 549, pages 365-369 and supplemental online content(extended data), Sep. 21, 2017, in its entirety.

While this disclosure is focused on metal powders, other embodiments aredirected to functionalization of polymer particles, ceramic particles,glass particles, carbon particles, or mixtures of different materials.

Functionalized feedstocks may be powder feedstocks. As intended herein,“powder feedstocks” refers to any powdered metal, ceramic, polymer,glass, composite, or combination thereof. In preferred embodiments, thepowder feedstocks are metals or metal-containing compounds, such as (butnot limited to) Al, Mg, Ni, Fe, Cu, Ti, V, Si, or combinations thereof,for example.

The nanoparticles or microparticles are typically a differentcomposition than the base powder. Nanoparticles or microparticles mayinclude metals, ceramics, cermets, intermetallic alloys, oxides,carbides, nitrides, borides, polymers, carbon, and combinations thereof,for example, or other materials which upon processing form one or moreof the aforementioned materials.

Generally speaking, the functionalized materials may contain one or morealloying elements selected from the group consisting of Si, Fe, Cu, Ni,Mn, Mg, Cr, Zn, V, Ti, Bi, Ga, Pb, or Zr. Other alloying elements may beincluded, such as (but not limited to) H, Li, Be, B, C, N, O, F, Na, P,S, Cl, K, Ca, Sc, Co, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Nb, Mo, Tc, Ru,Rh, Pd, Ag, Cd, In, Sn, Te, I, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au,Hg, Tl, Ce, Nd, and combinations thereof. These other alloying elementsmay function as grain refiners, as strength enhancers, as stabilityenhancers, or a combination thereof.

In some embodiments, the nanoparticles or microparticles contain one ormore elements selected from the group consisting of zirconium, tantalum,niobium, titanium, and combinations, oxides, nitrides, hydrides,carbides, or borides thereof. As a specific example pertaining tozirconium, the zirconium may be present as ZrH_(x) (x=0 to 4), i.e. inhydride form when x>0. An exemplary zirconium hydride is ZrH₂.

Powder particle sizes are typically between about 1 micron and about 1millimeter, but in some cases could be as much as about 1 centimeter.The powdered feedstock may be in any form in which discrete particlescan be reasonably distinguished from the bulk. The powder may be presentas loose powders, a paste, a suspension, or a green body, for example. Agreen body is an object whose main constituent is weakly bound powdermaterial, before it has been melted and solidified. The functionalizedpowder feedstocks may be converted into a geometric object, such as awire, by controlling melting and solidification. The geometric objectmay itself be a functionalized precursor feedstock for another process,or may be a final part.

Powder particles may be solid, hollow, or a combination thereof.Particles can be made by any means including, for example, gasatomization, milling, cryomilling, wire explosion, laser ablation,electrical-discharge machining, or other techniques known in the art.The powder particles may be characterized by an average aspect ratiofrom about 1:1 to about 100:1. The “aspect ratio” means the ratio ofparticle length to width, expressed as length:width. A perfect spherehas an aspect ratio of 1:1. For a particle of arbitrary geometry, thelength is taken to be the maximum effective diameter and the width istaken to be the minimum effective diameter.

In some embodiments, particles within a powder feedstock are rod-shapedparticles or domains resembling long sticks, dowels, or needles. Theaverage diameter of the rod-shaped particles or domains may be selectedfrom about 5 nanometers to about 100 microns, for example. Rods need notbe perfect cylinders, i.e. the axis is not necessarily straight and thediameter is not necessarily a perfect circle. In the case ofgeometrically imperfect cylinders (i.e. not exactly a straight axis or around diameter), the aspect ratio is the actual axial length, along itsline of curvature, divided by the effective diameter, which is thediameter of a circle having the same area as the average cross-sectionalarea of the actual shape.

“Surface functionalization” refers to a surface modification on thepowdered materials, which modification affects the solidificationbehavior (e.g., solidification rate, yield, grain quality, heat release,etc.) of the powder materials. In various embodiments, a powderedmaterial is functionalized with about 1%, 2%, 5%, 10%, 15%, 20%, 25%,30%, 40%, 50%, 60%, 70%, 80%, 85%, 90%, 95%, 99%, or 100% of the surfacearea of the powdered material having surface-functionalizationmodifications. The surface modification maybe a surface-chemistrymodification, a physical surface modification, or a combination thereof.

In some embodiments, the surface functionalization includes ananoparticle coating and/or a microparticle coating. The nanoparticlesand/or microparticles may include a metal, ceramic, polymer, or carbon,or a composite or combination thereof. The surface functionalizationpreferably includes nanoparticles that are chemically or physicallydisposed on the surface of the powder materials.

Nanoparticles are particles with the largest dimension between about 1nm and about 5000 nm. A preferred size of nanoparticles is about 2000 nmor less, about 1500 nm or less, or about 1000 nm or less. In someembodiments, nanoparticles are at least 50 nm in size. Microparticlesare particles with the largest dimension between about 1 micron andabout 1000 microns. The ratio of average particle size of microparticlesto average particle size of nanoparticles may vary, such as about 1,about 10, about 10², about 10³, about 10⁴, or about 10⁵. In someembodiments, this ratio is from about 10 to about 1000.

The nanoparticle or microparticle size may be selected based on thedesired final properties. Generally speaking, nanoparticles arepreferred over microparticles for functionalization. However, referencesin this specification to nanoparticles should be understood to includeembodiments in which microparticles are used in place of, or in additionto, nanoparticles.

Nanoparticles or microparticles may be spherical or of arbitrary shapewith the largest dimension typically not exceeding the above largestdimensions. An exception is structures with extremely high aspectratios, such as carbon nanotubes in which the dimensions may include upto 100 microns in length but less than 100 nm in diameter. Thenanoparticles or microparticles may include a coating of one or morelayers of a different material. Mixtures of nanoparticles andmicroparticles may be used. In some embodiments, microparticlesthemselves are coated with nanoparticles, and themicroparticle/nanoparticle composite is incorporated as a coating orlayer on the powder material particles.

Nanoparticles or microparticles may be attached using electrostaticforces, Van der Waals forces, chemical bonds, physical bonds, and/or anyother force. A chemical bond is the force that holds atoms together in amolecule or compound. Electrostatic and Van der Waals forces areexamples of physical forces that can cause bonding. A physical bond is abond that arises when molecular entities become entangled in space.Typically, chemical bonds are stronger than physical bonds. Chemicalbonds may include ionic bonds, covalent bonds, or a combination thereof.

The nanoparticles may be generated ex situ, generated in situ, or acombination thereof. Ex situ generation of nanoparticles means that thenanoparticles are introduced to the powder surface already in the formof nanoparticles, from a prior step. In situ generation of nanoparticlesmeans that nanoparticles are made from a precursor that has already beenapplied, or is continuously applied, to the powder surface, within theagitated pressure vessel. For example, nanoparticles may be generated insitu by pulse-wire discharge (wire explosion), solidification from avapor phase containing nanoparticle precursors, vaporization followed bysolidification, or other means.

Assembly aids may be incorporated. Assembly aids enhance the retentionof nanoparticles on surfaces of the powder particles. In particular,assembly aids may enhance the chemical kinetics of nanoparticleassembly, the thermodynamics of nanoparticle assembly, or the diffusionor mass transport of nanoparticle assembly, for example. Assembly aidsmay be selected from the group consisting of surfactants, salts,dissolved ions, charged molecules, polar or non-polar solvents,hierarchically sized particulates, surface etchants for surface texture,and combinations thereof. For example, surfactants may reduce surfacetension between nanoparticles and powder surfaces, resulting in betterwetting and assembly. Salts or ions may alter the surface charge of thenanoparticles or powder surfaces, resulting in ionic bonds that enhancethe assembly. Surface etchants may physically etch the surface of thepowder to promote adsorption of nanoparticles.

The nanoparticles may be in the form of a monolayer, a multilayer, orless than one monolayer (e.g., from about 1% to 100% of one monolayer)and may be uniform or non-uniform at the powder surfaces. The exemplarymaterials shown in FIGS. 3 to 5 suggest non-uniform particles(discontinuous coating), forming less than one monolayer on average.

Nanoparticles may act as grain refiners to give a unique microstructurefor a component ultimately produced from a nanofunctionalized metalpowder as provided herein. In some preferred embodiments, therefore, thesecond particles include grain-refining nanoparticles. Thegrain-refining nanoparticles may be present in a concentration of atleast 0.01 vol %, such as at least 0.1 vol %, at least 1 vol %, or atleast 5 vol %. In various embodiments, the grain-refining nanoparticlesare present in a concentration of about, or at least about, 0.1, 0.2,0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 vol %. The concentration of thegrain refiner(s) may be varied by adjusting the amount of grain refinersfunctionalized on the powder surface, and/or by adjusting theconcentration of functionalized micropowders versus non-functionalizedmicropowders in the final material. Routine experimentation can beperformed by a person of ordinary skill in the art to inform materialselection and concentration for the grain-refining nanoparticles.

The number of nanoparticles per microparticle can vary widely. Theaverage number of individual nanoparticles disposed on one microparticle(equivalently, the average number ratio of nanoparticles to powdermicroparticles) may be about 10, about 10², about 10³, about 10⁴, about10⁵, or about 10⁶, for example. The nanoparticle distribution on thepowder particle surface can vary, as shown in FIGS. 3 to 5 . In someembodiments, surface regions contain a relatively higher concentrationof nanoparticles, which may be agglomerated at the surface in thoseregions.

The nanoparticle surface coverage may also vary widely, from about 1% to100%, in various embodiments. The nanoparticle surface coverage is theaverage area fraction of powder particles that is covered by assemblednanoparticles. For example, the nanoparticle surface coverage may beabout, or at least about, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%,80%, 90%, or 100%. Due to the small size of nanoparticles, benefits arepossible with less than 1% surface area coverage.

The selection of the coating/powder composition will be dependent on thedesired properties and should be considered on a case-by-case basis.Someone skilled in the art of material science or metallurgy will beable to select the appropriate materials for the intended use, based onthe information provided in this disclosure.

In some embodiments, at least one nanoparticle is lattice-matched towithin ±5% compared to powder feedstock without the nanoparticle.Preferably, the nanoparticle is lattice-matched to within ±2%, morepreferably to within ±0.5%, compared to a powder feedstock without thenanoparticle.

In some embodiments, surface functionalization is in the form of acontinuous coating or an intermittent coating. A continuous coatingcovers at least 90% of the surface, such as about 95%, 99%, or 100% ofthe surface (recognizing there may be defects, voids, or impurities atthe surface). An intermittent coating is non-continuous and covers lessthan 90%, such as about 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, 5%, 2%,1%, or less of the surface. An intermittent coating may be uniform(e.g., having a certain repeating pattern on the surface) or non-uniform(e.g., random).

In general, a functionalization coating may be continuous ordiscontinuous. The coating may have several characteristic features. Inone embodiment, the coating may be smooth and conformal to theunderlying surface. In another embodiment, the coating may be nodular.The nodular growth is often characteristic of kinetic limitations ofnanoparticle assembly. For example, the coating may look likecauliflower or a small fractal growing from the surface. These featurescan be affected by the underling materials, the method of coating,reaction conditions, etc.

In some embodiments, microparticles (rather than nanoparticles) coatmicropowders or macropowders. The micropowder or macropowder particlesmay include ceramic, metal, polymer, glass, or combinations thereof. Themicroparticles (coating) may include metal, ceramic, polymer, carbon, orcombinations thereof. In the case of microparticles coating othermicropowders or macropowders, functionalization preferably means thatthe coating particles are of significantly different dimension(s) thanthe base powder. For example, the microparticles may be characterized byan average dimension (e.g., diameter) that is less than 20%, 10%, 5%,2%, or 1% of the largest dimension of the coated powders.

The materials and methods disclosed herein may be applied to additivemanufacturing as well as joining techniques, such as welding. Certainunweldable metals, such as high-strength aluminum alloys (e.g., aluminumalloys Al 7075, Al 7050, or Al 2199) would be excellent candidates foradditive manufacturing but normally suffer from hot cracking. Theprinciples disclosed herein allow these alloys to be processed withsignificantly reduced cracking tendency. In particular, thenanofunctionalized metal powder may be converted to a metal alloy objectthrough various means, such as additive manufacturing or other metalprocessing, wherein the metal alloy object is characterized by a uniquemicrostructure.

A unique microstructure may be produced in a wide variety of alloysystems, as well as from metal processing beyond additive manufacturing.Incorporation of previously impossible concentrations and types of grainrefiners is possible, in this disclosure, due to grain-refining elementsbeing disposed on surfaces of base powder. This process utilizesfunctionalization to incorporate grain refiners directly at the site ofmelting, negating the need for expensive processing and making use ofcommercially available alloy powders. This technique is in contrast toincorporation of grain refiners into the internal regions of powderparticles, which requires extremely high temperatures during gasatomization. Such high temperatures can cause volatility of certainalloying elements (including Zn, Mg, and Li), and can be damaging toequipment due to the high reactivity of some elements in metal alloys.

In some embodiments, a metal alloy microstructure (produced startingwith a functionalized metal powder) is “substantially crack-free” whichmeans that at least 99.9 vol % of the metal alloy contains no linear ortortuous cracks that are greater than 0.1 microns in width and greaterthan 10 microns in length. In other words, to be considered a crack, adefect must be a void space that is at least 0.1 microns in width aswell as at least 10 microns in length. A void space that has a lengthshorter than 10 microns but larger than 1 micron, regardless of width,can be considered a porous void (see below). A void space that has alength of at least 10 microns but a width shorter than 0.1 microns is amolecular-level gap that is not considered a defect.

Typically, a crack contains open space, which may be vacuum or maycontain a gas such as air, CO₂, N₂, and/or Ar. A crack may also containsolid material different from the primary material phase of the metalalloy. These sorts of cracks containing material (other than gases) maybe referred to as “inclusions.” The non-desirable material disposedwithin the inclusion may itself contain a higher porosity than the bulkmaterial, may contain a different crystalline (or amorphous) phase ofsolid, or may be a different material altogether, arising fromimpurities during fabrication, for example. Large phase boundaries canalso form inclusions. Note that these inclusions are different than thedesirable nanoparticle inclusions that may form during additivemanufacturing.

The metal alloy microstructure may be substantially free of porousdefects, in addition to being substantially crack-free. “Substantiallyfree of porous defects” means at least 99 vol % of the metal alloycontains no porous voids having an effective diameter of at least 1micron.

Porous defects may be in the form of porous voids. Typically, a porousvoid contains open space, which may be vacuum or may contain a gas suchas air, CO₂, N₂, and/or Ar. Preferably, at least 80 vol %, morepreferably at least 90 vol %, even more preferably at least 95 vol %,and most preferably at least 99 vol % of the metal alloy contains noporous voids having an effective diameter of at least 1 micron. A porousvoid that has an effective diameter less than 1 micron is not typicallyconsidered a defect, as it is generally difficult to detect byconventional non-destructive evaluation. Also preferably, at least 90vol %, more preferably at least 95 vol %, even more preferably at least99 vol %, and most preferably at least 99.9 vol % of the metal alloycontains no larger porous voids having an effective diameter of at least5 microns.

In some embodiments, the metal alloy microstructure (produced startingwith a functionalized metal powder) has “equiaxed grains” which meansthat at least 99 vol % of the metal alloy contains grains that areroughly equal in length, width, and height. In the metal alloy, crystalsof metal alloy form grains in the solid. Each grain is a distinctcrystal with its own orientation. The areas between grains are known asgrain boundaries. Within each grain, the individual atoms form acrystalline lattice. Equiaxed grains result when there are manynucleation sites arising from grain-refining nanoparticles contained inthe metal alloy microstructure.

The equiaxed grains, and reduction or elimination of cracks, in thefinal microstructure results from the presence of grain-refiningnanoparticles in the initial functionalized metal powder (in powder formor other geometric form).

Some variations provide a solid metal alloy object comprising at leastone solid phase (i) containing a functionalized powdered material asdescribed, or (ii) derived from a liquid form of a functionalizedpowdered material as described. The solid metal alloy object may be ageometric object (e.g., wire or rod) that is useful for metalprocessing, instead of powder feedstock. The solid metal alloy objectmay be subjected to powder metallurgy processing techniques including,but are not limited to, hot pressing, low-pressure sintering, extrusion,metal injection molding, and additive manufacturing.

In this detailed description, reference has been made to multipleembodiments and to the accompanying drawings in which are shown by wayof illustration specific exemplary embodiments of the invention. Theseembodiments are described in sufficient detail to enable those skilledin the art to practice the invention, and it is to be understood thatmodifications to the various disclosed embodiments may be made by askilled artisan.

Where methods and steps described above indicate certain eventsoccurring in certain order, those of ordinary skill in the art willrecognize that the ordering of certain steps may be modified and thatsuch modifications are in accordance with the variations of theinvention. Additionally, certain steps may be performed concurrently ina parallel process when possible, as well as performed sequentially.

All publications, patents, and patent applications cited in thisspecification are herein incorporated by reference in their entirety asif each publication, patent, or patent application were specifically andindividually put forth herein.

The embodiments, variations, and figures described above should providean indication of the utility and versatility of the present invention.Other embodiments that do not provide all of the features and advantagesset forth herein may also be utilized, without departing from the spiritand scope of the present invention. Such modifications and variationsare considered to be within the scope of the invention defined by theclaims.

What is claimed is:
 1. A method for producing a functionalized powderfor additive manufacturing or welding, said method comprising: (a)introducing a plurality of first particles into an agitated pressurevessel under an inert atmosphere, wherein said first particles have anaverage first-particle size from about 1 micron to about 1 millimeter;(b) introducing a plurality of second particles into said agitatedpressure vessel under said inert atmosphere, wherein said secondparticles are nanoparticles with an average second-particle size fromabout 1 nanometer to about 5000 nanometers, wherein said secondparticles are compositionally different than said first particles, andwherein said second particles are selected from the group consisting ofzirconium hydrides, tantalum hydrides, niobium hydrides, titaniumhydrides, and combinations thereof; (c) after steps (a) and (b),introducing a fluid into said agitated pressure vessel, wherein saidfluid dissolves or suspends both of said first particles and said secondparticles, and wherein said agitated pressure vessel is operated at avessel pressure from about 2 bar to about 200 bar; (d) after step (c),in said agitated pressure vessel and at said vessel pressure, reactingsaid second particles with said first particles to generate afunctionalized powder containing said second particles disposed ontosurfaces of said first particles; (e) after step (d), releasing saidfluid from said agitated pressure vessel; and (f) after step (e),recovering said functionalized powder from said agitated pressurevessel.
 2. The method of claim 1, wherein said fluid is selected fromthe group consisting of carbon dioxide, nitrous oxide, C₁-C₄hydrocarbons, C₁-C₄ oxygenates, and combinations thereof.
 3. The methodof claim 1, wherein said fluid includes carbon dioxide in a vapor stateand/or a liquid state within said agitated pressure vessel.
 4. Themethod of claim 1, wherein said fluid includes carbon dioxide in asupercritical state within said agitated pressure vessel.
 5. The methodof claim 1, wherein said fluid is carbon dioxide in vapor form and/orliquid form.
 6. The method of claim 1, wherein said reacting said secondparticles with said first particles is conducted at a reactiontemperature from about 10° C. to about 200° C.
 7. The method of claim 1,wherein said reacting said second particles with said first particles isconducted for a reaction time from about 10 minutes to about 50 hours.8. The method of claim 1, wherein said method is operated in batch. 9.The method of claim 1, wherein said method is operated continuously orsemi-continuously.
 10. The method of claim 1, wherein said firstparticles are selected from the group consisting of metal particles,intermetallic particles, ceramic particles, and combinations thereof.11. The method of claim 1, wherein said first particles contain one ormore metals selected from the group consisting of aluminum, iron,nickel, copper, titanium, magnesium, zinc, silicon, lithium, silver,chromium, manganese, vanadium, bismuth, gallium, lead, and combinationsthereof.
 12. The method of claim 1, wherein said second particles areselected from the group consisting of metal particles, intermetallicparticles, ceramic particles, and combinations thereof.
 13. The methodof claim 1, wherein said inert atmosphere is argon or nitrogen.
 14. Themethod of claim 1, wherein step (c) comprises introducing a fluidprecursor into said agitated pressure vessel, and then sealing saidagitated pressure vessel, and then converting said fluid precursor,within said agitated pressure vessel, to said fluid.
 15. The method ofclaim 14, wherein said fluid precursor is solid carbon dioxide, whereinsaid fluid is carbon dioxide, and wherein said solid carbon dioxidemelts or sublimates within said agitated pressure vessel to form saidcarbon dioxide in vapor form and/or liquid form.
 16. The method of claim1, wherein said second particles are in the form of a discontinuouscoating on said first particles.
 17. The method of claim 1, wherein saidfunctionalized powder is melted and resolidified in anadditive-manufacturing process.
 18. The method of claim 1, wherein saidfunctionalized powder is melted and resolidified in a welding process.